Certain tris(difluoramino)substituted ammonium perchlorates

ABSTRACT

A compound of the formula   WHEREIN N IS A NUMBER FROM 1 TO 3, M IS 3-N, P IS FROM 1 TO 11, R IS FROM 1 TO 3, S IS 3-R, X IS 1 TO 3 AND Y IS 4-X, PROVIDED THAT AT LEAST ONE OF R AND X IS 1.

United States Patent Ronald A. Mitsch St. Paul;

Joseph La Mar Zollinger, Woodbury Township, Washington County; DouglasH. Dybvigfi St. Paul; Charles D. Wright, White [72] Inventors Bear Lake,all oi Minn.

[2| Appl. No. 540,143

[22] Filed Mar. 29, 1966 [45] Patented Nov. 30, 1971 [73] AssigneeMinnesota Mining and Manufacturing Company St. Paul, Minn.

Continuation-impart of application Ser. No. 286,881, May 29, 1963, nowPatent No. 3,624,156, dated Nov. 30, 1971. This application Mar. 29,1966, Ser. No. 540,143

[54] CERTAIN TRIS(DIFLUORAMINO)SUBSTITUTED AMMONIUM PERCHLORATES 19Claims, No Drawings 1521 U.S.Cl 260/584 c, 149/109, 260/564 R PrimaryExaminer Leland A. Sebastian Anorneys- Frank A. Steldt, Donald C. Gippleand Temple Clayton ABSTRACT: A compound of the formula I[(NF1)IIC muLCHJNHfiClOr wherein n is a number from 1 to 3, m is 3-n,p is from i toI], r is from i to 3, sis 3 r, x is l to 3 and y is 4-x. provided thatat least one ofr and x is l.

CERTAIN TRIS(DIFLUORAMINO)SUBSTITUTED AMMONIUM PERCHLORATES Thisapplication is a continuation-in-part of copending application Ser. No.286,881, filed May 29, 1963.

This invention relates to novel ionic fluorinated oxidant compounds andto a process for their preparation.

Fluorinated oxidants have been known heretofore, those of high oxidizingpower being of particular use in propellants and explosives. Previouslyknown fluorinated oxidants of high oxidizing power have generally beenrelatively volatile, hydrophobic and somewhat miscible with polymericbinders commonly used in composite propellants, e.g., hydrocarbon,fluorocarbon and cellulosic binders. These properties have often beendisadvantageous. In solid propellants, for example, essentiallynonvolatile constituents are desired for ease and safety of fabricationand storage and dependability of performance on firing. Further, anymiscibility of the oxidant with the polymeric binder in a compositepropellant composition often tends to weaken the grain physically and/orincrease the impact sensitivity thereof: Further, the volatility andhydrophobicity (i.e. water insolubility) of the fluorinated oxidantshave often been disadvantageous with respect to their use as bleaches.

It is therefore an object of this invention to provide certainnonvolatile solid ionic compounds containing from one to ninedifiuoramino groups. It is another object of the invention to providefluorinated oxidizing agents which have high degrees of compatibilitywith (i.e. can be easily used with) complementary constituents ofhigh-performance solid propellant compositions such as polymericbinders. It is a further object of the invention to provide a processfor the preparation of certain fluorinated oxidizing agents of lowvolatility which have very low solubility in polymeric binders.

in accordance with the above and other objects of the invention, it hasbeen found that certain compounds having the formula wherein n is anumber from 1 to 3, m is 3n, p is from 1 to 11, r is from I to 3, s is3r, x is from 1 to 3 and y is 4-x, provided that at least one of r and xis 1, can be produced. They are prepared by direct fluorination ofadducts of perfluoroformamidine, perfluoroguanidine orperfluoromethylenimine with an alkanolamine perchlorate according to thefollowing general reaction procedure:

wherein n, m, p, r, s, x and y are as previously defined.

Compounds of the invention in which n is 3 form a generally preferredgroup, and those in which n is 3 and p is a low number (ordinarily 1)form a more preferred group for use in propellant compositions sincethey fonn relatively high specific impulse propellants. Those compoundsin which x and r are both 1 form another preferred group in that theyare easily prepared.

Methods of producing perfluoroformamidine and perfluoroguanidine aredisclosed in the copending application of our coworkers. Ser. No.99,632, filed Mar. 30, 1961. Perfluoromethylenimine and the alkanolamineperchlorates are known compounds.

The properties of the fluorinated oxidants must of course be taken intoconsideration and overheating of sensitive compounds must be avoided.Many of the compounds of the invention have a very high N-F content andmay explode with high energy release. Caution must be exercised duringthe preparation and manipulation of these products such as performingoperations behind suitable shields and wearing protective jackets,gloves and ear plugs to prevent personal injury in the event ofexplosions. The occasional explosion of perfiuoroguanidine when frozento l96 C. during vacuum transfers is largely avoided by transferring invacuo at temperatures above the melting point of perfluoroguanidine,e.g., -l l l C., using a fiuorotrichloromethane slush bath as thecooling medium.

Except for the foregoing, however, the process of the invention can becarried out by methods generally known to those skilled in the art.

Once the compounds of the invention have been prepared, a number ofpurification techniques can be used. Their high stability toward air andmoisture permits the use of the conventional techniques ofrecrystallization, solvent extraction, ion exchange and liquid columnchromatography. The latter technique is of great value when coupled withthin layer chromatography techniques which permit the choice of propersupports and solvents using very small quantities. In some cases,sublimation is of value in the purification of these compounds.

The compounds of the invention are solids having strong oxidizing power.They are useful as explosives and for incorporation into propellants asthe oxidant component and for other applications in which theiroxidizing power can be utilized, as, for example, bleaching agents andthe like.

A preferred compound of the invention is 2- [tris(difluoramino)methoxy]ethylammonium perchlorate, (NF,) COCH CH, NH 'C1O which can be producedby the direct fluorination of the adduct of perfluoroguanidine andethanolamine perchlorate. The 2-[tris(difiuoroamino)m ethony]ethylammonium perchlorate thus prepared melts with decomposition atabout 218:3 C., is soluble in water and is compatible with and isrelatively insoluble in hydrocarbons, e.g. heptane, cyclohexene,carboxy-terminated poly-butadiene (a commonly used binder forpropellants), and fiuorochemical-type polymers. The calculated specificimpulse of 2-[tris(difluoramino)methoxy] ethylammonium perchlorate as amonopropellant and as a solid propellant admixed with lithium metal anda fluorochemical binder are given in the following table:

The following examples will more specifically illustrate the Vpreparation of the compounds of the invention. All parts are by weightunless otherwise specified.

EXAMPLE 1 into a 5 ml. reactor fitted with a Fischer-Porter Teflon valveare added 0.162 g. (l l0 moles) of ethanolamine perchlorate and lmilliliter of acetonitrile (0.25 percent H 0). After degassing, 0.360 g.(2.42Xl0moles) of perfluoroguanidine is condensed into the reactor at 119 C. The mixture is allowed to warm to and remain at room temperatureover a 2-week period. The reaction is accelerated by the use of basiccatalysts such as urea, triethylamine, etc. With urea as a catalyst, forexample, the reaction is complete in about I day.

The volatile contents of the reactor are then separated by fractionaldistillation-condensation techniques, and 1.26X10 moles ofperfluoroguanidine are recovered. The semisolid residue in the reactoris subjected to reduced pressure for 4 hours at room temperature andthen dissolved in acetonitrile. A fluorine nuclear magnetic resonancespectrum on this solution shows the major absorption at 22.0 l (NH) anda doublet at +l4l.l (NFH). The only other absorption is at The colorlesstrifluoroethanol solvent is withdrawn from the reactor by means of acapillary syringe and placed in a nuclear magnetic resonance tube fittedwith a Fischer-Porter valve. Evaporation in vacuo affords 0.103 g. of acolorless glass which is divided in half. A 0.051 g. portion of thecrude product is pumped on for an additional 22 hours at roomtemperature to give 0.043 g. of a semisolid which is dissolved inacetonitrile. The F" n.m.r. spectrum exhibits a major band at 24.0 I(NI-" and a less intense band at +l49.l 4 (BF,). Three other very minorabsorptions are present at 20. l --l9.5 and +74.3 1

The salt is purified by liquid column chromatography on a silica gelcolumn utilizing the following order of solvents:

chlorofonn, 50 50 chloroform-ethyl acetate, ethyl acetate 25 andethanol. The product, ClO,'NH Cl-l CH OC( NF which is obtained byevaporation of the ethyl acetate eluate, is a colorless solid meltingwith decomposition at about 215 C. 22 1 C.

Analysis calculated for C -,H ClF N.,O C, 11.0; F, 34.7;

m.w., 32 l Found: C, l 1.5; F, 33.8; m.w., 32].

The colorless solid has a density of about 1.8 g./cc. and an impactsensitivity of about 6 kg.-cm.

EXAMPLE 2 In a 15 mL-capacity dry glass reactor containing a stirringbar and fitted with a polytetrafluoroethylene needle valve are placedl.5 g. (5 millimole) of 5 HO(CH ),,NH *ClO, 0.030

g. (0.5 millimole) of urea catalyst, and 5 ml. of dry acetonitrile. Themixture is degassed at ll0 C. (CFCl: slush) and [.0 g. (6.5 millimole)of perfluoroguanidine is transferred under vacuum to the reactor at thistemperature.

The reaction mixture is allowed to warm to room temperature in theclosed reactor and is then stirred magnetically for l5 hours.

Fluorine nuclear magnetic resonance (F n.m.r.) spectral analysis of theliquid phase reveals a good conversion to HFNC(NF ,ch),,NH;,*ClO,'(-2O.8for NF and 141.2 1 doublet, for F of NFH). Peaks at42.6 (NF and +46.2 l (=NF) are due to a small amount of FN=C(NF )O (Cl-l),,NH ClO{ resulting from a loss of HNF from the principal product.

Fluorination is carried out by introducting a 3 percent F 97 percent Nstream at a rate of 70 ml. per minute into the solution whilemaintaining the glass reactor at 30 C. A total of about 20 millimoles offluorine is introduced over a period of 4 hours. The solution is purgedwith nitrogen gas while warming to room temperature.

Purification of the product is effected by a solvent extracmethanolsolution afiords nearly pure product as observed by infrared analysisand oxidizing power. A carbonyl containing impurity is removed byshaking the product with a benzenewater mixture and evaporating thewater layer. in this manner the pure solid product is obtained.

The desired product can also be purified by column chromatography usingsilica gel as the column absorbent and chloroform-ethyl acetate as theeluting solvents. EXAMPLE 3 According to the procedure of example 2,diethanol ammonium perchlorate (0.40 g., 2.0 millimoles), urea (0.024g., 0.4 millimole) and perfluoroguanidine (0.90 g., 6 millimoles) arereacted in 5 ml. of acetonitrile solution. After stirring the reactionfor 48 hours at room temperature, volatile components, including excessperfluoraguanidine, are removed by subjecting the reaction mixture toreduced pressure for 1 minute and trapping the gases at 1 10 C. fordiscard. The acetonitrile solution, which now contains [HFNC(NF,) OCH CHNH C1O is subjected to a dilute fluorine stream at 30 C., as describedin example 2, until 25 millimoles of F have been delivered. Theresulting product, [(NF COCH CH NH *CIO is recovered from theacetonitrile solution and purified by solvent extraction orchromatography techniques as described in example 2.

EXAMPLE 4 According to the procedure of example 2, the followingreagents are reacted in 4 ml. of acetonitrile solution: triethanolammonium perchlorate (0.25 g., 1.0 millimole), urea (0.018 g., 0.3millimole) and perfluoroguanidine (0.9 g., 6 millimole).

After stirring at room temperature for 3 days in the closed glassreactor, the excess perfluoroguanidine is removed under reduced pressure(example 3 The residual acetonitrile solution containing [HFNC(NF OCH CHNH*ClOf is fluorinated at 30 C. with a dilute fluorine gas stream until20 millimoles of fluorine have been delivered. The resulting product[(NF, cocn cu, l Nl-FClQ, is purified, preferably by columnchromatography as described in example 2.

EXAMPLE 5 According to the procedure of example 2, the following re-.agents are reacted in 4 ml. of dry acetonitrile solution: the

perchlorate salt of 2-amino-2-(hydroxymethyl l ,3- propanediol (0.22 g.,1.0 millimole), urea catalyst (0.0[8 g., 0.3 millimole) and excessperfluoroguanidine (0.9 g., 6 millimoles).

After stirring at room temperature for 3 days, excess perfluoroguanidineand other gases are removed by brief subjection to reduced pressure. Theacetonitrile solution containing the adduct [HFNC(NF hoCH l CNl-lfClo,is fluorinated at 20C. with a 3 percent F (97 percent N stream at aboutml. per minute until 20 millimoles of F have been bubbled through thesolution. The main fluorinated product, [(NF COCH is purified by columnchromatography employing a silica gel absorbent and chloroform-ethylacetate as solvents.

reactants to recover the indicated products:

Fluorimlno reactant Perchlorate reactant Product HO (CH2) zNII Cl04[(NFz) (F) 20 O (C H2) :NHsEIOt In the fluorine nuclear magneticresonance spectra herein, CFCl is employed as an internal standard asdescribed by Filipovich and Tiers, Journal of Physical Chemistry, Vol.63,

pp. 761-762, 1959, the 4" values defined by those authorsbeing givensimply as d values.

The addition of the fluorimino compound in the process of the inventionis preferably carried out in the presence of an anhydrous solvent suchas acetonitrile or CFCl and a basic catalyst such as urea,triethylamine, etc. The addition reaction is preferably carried out inthe range of 1 C. to +50 C. When perfluoromethylenimine orperfluoroformamidine is utilized. low temperatures are especiallyimportant to avoid undesirable side reactions.

What is claimed is:

l. A compound of the formula F,)no FmO(CHz)p]rCH.]NH +C1O4' wherein n isa number from I to 3, m is 3-n,p is from 1 to 11, r is from 1 to 3, s is3r, x is l to 3 and y is 4-1:, provided that at least one of r and x isl.

2. A compound according to claim 1 wherein n is 3.

3. A compound according to claim 1 wherein p is l.

4. A compound according to claim 2 wherein r is i.

5. A compound according to claim 1 wherein x is l.

6. A compound according to claim 4 wherein x is l.

7. A compound according to claim 1 wherein r is 3.

8. The compound having the formula [(NF CO(CH,) NHfClbf 9. The compoundhaving the formula [(NF CO(CH NHJCIO 10. The compound having the formula[(NF -,COCH uvna 11. The compound having the formula [(NF -,CO(CHNl-PCIOB4' 12. The compound having the formula [(NF -,CO(CH 2 z f 13. Aprocess for the preparation of a compound of the formula wherein n is anumber from i to 3, m is 3n, p is from 1 to H, r is from 1 to 3, s is3-r, x is l to 3 and y is 4-x, provided that at least one of r and x isl, which comprises interreacting an alkanolamine perchlorate of theformula 1) DL -L W F with a compound of the formula NF,),,,C( F ),,.=NFto form the adduct subjecting this adduct to direct fluorination andrecovering the desired product.

14. A process according to claim 13 wherein n is 3.

15. A process according to claim 13 wherein p is l.

16. A process according to claim 14 wherein r is l.

17. A process according to claim 13 wherein x is 1.

18. A process according to claim 13 for the preparation of2-[tris(difluoramino)methoxy]ethylammonium perchlorate which comprisesinterreacting perfluoroguanidine and ethanolamine perchlorate,subjecting the resulting product to direct fluorination and recoveringthe desired product.

UNITED STATES PATENT OFFICE CERTHHCATE 0F CORRECTION e Patentlkn3,62u,156 Datmi November 30, 1971 lnvmnorun Ronald A. Mitsch, JosephLaMar Zollinger, Douglas H.

Dybvig and Charles D. Wright It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 37, 1st formula, "[[(NF CF O(CH CH ]NH ClO should be"-[[(NF CF O(CH) CHg] NHClO column 1, 2nd formula 3rd line, "[[(NF CFO(CH2) CH] NHClO" should be --[[(NF cF 0(cH cHs] NH;c10

Column 2, lines 31 and 32, Z-[tris(difluoroamino)methony]" should be-2-[tris(difluoramino)methoxy]-- Column 2, line 61, "10 should be -10'Column 3, line 50, HFNC(NF ,ch NH ClO should be -HFNC(NF O(CH NH ClOuColumn a, lines 19 & 20, [HFNc(NF 0cH cH NH +c10 should be --[HFNC(NFOCH CH NH? ClO Column A, line 58, "COCH CNH should be --COCH CNHCl0EColumn A, in the Table at the bottom of the page under Fluoriminoreactant, first formula "((NF )C(F)=NF" should be --(NF )C(F)=NF- Column4, Table under Produc, first formula "[NF (F)CO(CH) H Cl0 should be -6RM PO 1050 (1D USCOMM-DC 60376-F'69 9 U 5, GOVERNMENT PIHH'HNG OFFICEI989 0-366-334 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTIONPatent No. 3, 5 Dated November 30, 197

Page 2 lnventofls) Ronald A. Mitsch, Joseph LaMar Zollinger, Douglas H.

Dybvig and Charles D. Wright It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 4, in the Table at the bottom of the page under Product, secondformula.

(NF2) (F) CO(CH H 6lO should be (NT- )(F) co(c1-1 ]ih1 6lo Claim 1,formula, "[[(NF cF o(c1-1 c1f ]m;clo should be clalm 8, formula, (NFc0(cH ]NH clb should be (NF CO(CH ]NH Gl0 Claim 9, formula, (NF co(oH]NH +clo"' (NF CO(CH ]NHClO Claim 10, formula, (NF2)3COCH2J3CNH3+CIO'should be (NF2)3COCH2]3CNH;CJ.O4-

should be Claim 11, formula, NF co 0 NH Cl0B'4 should be (NF C0(CHNI-f"(3lO Claim 12, formula, (NF2)3C0(CH2)2]2NH2+4 should be M PO-1050(IO-69) 0.5 GOVERNMENT PRINTING OFFICE I969 0-385-334 UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Page 3 Patent No. 3,62, 1556Dated November 30, 1971 Inventofls) onald A. Mitsch Jose h LaMar Zolliner Do las H.

Dybvig and Charles D. Wright It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Claim 13, first formula, "[[(NF CF 0(CI-I CH ]NH ClO should be "[[(NF CF0(CH CH NI-IClO Signed and sealed this 27th day of June 1972.

(SEAL) Attest EDWARD M.F'LETCHER,JR. ROBERT GOTTSCHALK Attesting OfficerCommissioner of Patents USCOMM-DC 60375-P69 fi U 5. GOVERNMENT PRINTINGOFFJCfi f 19.9 0-366-334

2. A compound according to claim 1 wherein n is
 3. 3. A compound according to claim 1 wherein p is
 1. 4. A compound according to claim 2 wherein r is
 1. 5. A compound according to claim 1 wherein x is
 1. 6. A compound according to claim 4 wherein x is
 1. 7. A compound according to claim 1 wherein r is
 3. 8. The compound having the formula ((NF2)3CO(CH2)2)NH3 ClO4
 9. The compound having the formula ((NF2)3CO(CH2)11)NH3 ClO4
 10. The compound having the formula ((NF2)3COCH2)3 CNH3 ClO4
 11. The compound having the formula ((NF2)3CO(CH2)2)3NH ClO4
 12. The compound having the formula ((NF2)3CO(CH2)2)2NH2 ClO4
 13. A process for the preparation of a compound of the formula wherein n is a number from 1 to 3, m is 3-n, p is from 1 to 11, r is from 1 to 3, s is 3-r, x is 1 to 3 and y is 4-x, provided that at least one of r and x is 1, which comprises interreacting an alkanolamine perchlorate of the formula with a compound of the formula (NF2)n-1C(F)m NF to form the adduct subjecting this adduct to direct fluorination and recovering the desired product.
 14. A process according to claim 13 wherein n is
 3. 15. A process according to claim 13 wherein p is
 1. 16. A process according to claim 14 wherein r is
 1. 17. A process according to claim 13 wherein x is
 1. 18. A process according to claim 13 for the preparation of 2-(tris(difluoramino)methoxy)ethylammonium perchlorate which comprises interreacting perfluoroguanidine and ethanolamine perchlorate, subjecting the resulting product to direct fluorination and recovering the desired product.
 19. A process according to claim 13 for thE preparation of 2-(tris(difluoramino)methoxy)undecylammonium perchlorate which comprises interreacting perfluoroguanidine and undecanolamine perchlorate, subjecting the resulting product to direct fluorination and recovering the desired product. 